4054 J. Agric. Food Chem., Vol. 45, No. 10, 1997
Straubinger et al.
(1H, dd, J ) 12.0, 2.5, HaC6′), 4.25 (1H, dd, J ) 12.0, 5.0, Hb-
C6′), 4.74 (1H, q, J ) 6.5, HC9), 4.86 (1H, d, J ) 8.0, HC1′),
5.00 (1H, m, HC3), 5.03 (1H, dd, J ) 9.5, 8.0, HC2′), 5.10 (1H,
C8), 129.0 (C5/C7), 138.5 (C3), 20.6-20.7 and 169.4-170.4
(four acetates).
(2E)-2,6-Dimethyl-6-hydroxyocta-2,7-dienyl-O-â-D-glucopy-
ranoside (7) and (2Z)-2,6-dimethyl-6-hydroxyocta-2,7-dienyl-
O-â-D-glucopyranoside (8) were isolated as tetraacetates 7a
(1.6 mg) and 8a (1.2 mg). The known diol glucosides (Tschesche
et al., 1977; Strauss et al., 1988; Schwab et al., 1990) were
identified on the basis of the 1H NMR spectral data. 7a : DCI-
MS (reactant gas: NH3) pseudo-molecular ion at m/ z 518,
indicating a molecular mass of 500 (C24H36O11); 1H NMR (360
MHz, CDCl3, ppm, J in Hz) δ 1.30 (3H, s, CH3-C6), 1.60 (3H,
br s, CH3-C2), 1.60 (2H, m, H2C5), 1.89 (1H, s, -OH), 2.01-
2.09 (4 × 3H, 4s, four acetates), 2.09 (2H, m, H2C4), 3.65 (1H,
ddd, J ) 10.0, 5.0, 2.5, HC5′), 3.97 (1H, br d, J ) 12.0, HaC1),
4.14 (1H, dd, J ) 12.0, 2.5, HaC6′), 4.16 (1H, br d, J ) 12.0,
HbC1), 4.26 (1H, dd, J ) 12.0, 5.0, HbC6′), 4.48 (1H, d, J )
8.0, HC1′), 5.01 (1H, dd, J ) 9.5, 8.0, HC2′), 5.08 (1H, dd, J )
10.0, 9.5, HC4′), 5.09 (1H, dd, J ) 11.0, 1.5, HaC8), 5.20 (1H,
dd, J ) 9.5, 9.5, HC3′), 5.23 (1H, dd, J ) 17.5, 1.5, HbC8),
5.41 (1H, dt, J ) 7.5, 1.0, HC3), 5.92 (1H, dd, J ) 17.5, 11.0,
HC7).
dd, J ) 10.0, 9.5, HC4′), 5.21 (1H, dd, J ) 9.5, 9.5, HC3′); 13
C
NMR (126 MHz, CDCl3, ppm) δ 22.3 (CH3-C5) 23.1 (CH3-C9),
28.5 and 30.1 (2CH3-C1), 35.9 (C1), 37.3 (C4), 42.1 (C2), 62.0
(C6′), 67.5 (C9), 67.8 (C3), 68.4 (C4′), 71.8 (C2′), 71.9 (C5′), 73.0
(C3′), 84.0 (C7), 91.9 (C8), 98.9 (C1′), 123.2 (C6), 137.9 (C5),
20.6-21.4 and 169.3-170.7 (five acetates). Signals were
1
assigned by H-1H-COSY and HSQC (1H-13C-COSY) as well
as HMBC experiments.
3-Hydroxy-7,8-dihydro-â-ionol 9-O-â-D-glucopyranoside (2)
and 3-hydroxy-7,8-dihydro-â-ionol 3-O-â-D-glucopyranoside (3)
were isolated as their respective peracetates (2a and 3a ).
Spectral data for 2a (1.2 mg): UV (MeOH) λmax 209 nm; IR
(NaCl) ν 2918, 2850, 1757, 1448, 1366, 1224, 1036 cm-1; DCI-
MS (reactant gas: NH3) pseudo-molecular ion at m/ z 602,
indicating a molecular mass of 584 (C29H44O12); 1H NMR (360
MHz, CDCl3, ppm, J in Hz) δ 1.04 and 1.05 (2 × 3H, 2s, 2CH3-
C1), 1.14 (3H, d, J ) 6.5, CH3-C9), 1.49 (1H, dd, J ) 12.0, 2.0,
HaC2), 1.52 (2H, m, H2C8), 1.59 (3H, s, CH3-C5), 1.70 (1H, ddd,
J ) 12.0, 3.5, 2.0, HbC2), 1.93 (1H, dd, J ) 12.5, 6.5, HaC7),
1.98 (1H, dd, J ) 17.0, 2.5, HaC4), 2.00-2.07 (5 × 3H, 5s, five
acetates), 2.07 (1H, dd, J ) 12.5, 5.5, HbC7), 2.28 (1H, ddd, J
) 17.0, 5.5, 2.0, HbC4), 3.67 (1H, ddd, J ) 10.0, 5.0, 2.5, HC5′),
3.75 (1H, m, HC9), 4.12 (1H, dd, J ) 12.5, 2.5, HaC6′), 4.23
(1H, dd, J ) 12.5, 5.0, HbC6′), 4.55 (1H, d, J ) 8.0, HC1′),
4.96 (1H, dd, J ) 9.5, 8.0, HC2′), 4.98 (1H, m, HC3), 5.09 (1H,
8a : DCI-MS (reactant gas: NH3) pseudo-molecular ion at
1
m/ z 518, indicating a molecular mass of 500 (C24H36O11); H
NMR (360 MHz, CDCl3, ppm, J in Hz) δ 1.29 (3H, s, CH3-C6),
1.61 (2H, m, H2C5), 1.69 (3H, br s, CH3-C2), 1.77 (1H, br s,
-OH), 2.00-2.09 (4 × 3H, four acetates), 2.13 (2H, m, H2C4),
3.66 (1H, ddd, J ) 9.5, 4.0, 2.5, HC5′), 4.14 (1H, br d, J )
12.0, HaC1), 4.18 (1H, dd, J ) 12.0, 2.5, HaC6′), 4.28 (1H, br
d, J ) 12.0, HbC1), 4.29 (1H, dd, J ) 12.0, 4.0, HbC6′), 4.46
(1H, d, J ) 8.0, HC1′), 5.01 (1H, dd, J ) 9.5, 8.0, HC2′), 5.07
(1H, dd, J ) 11.0, 1.5, HaC8), 5.12 (1H, dd, J ) 9.5, 9.5, HC4′),
5.19 (1H, dd, J ) 9.5, 9.5, HC3′), 5.21 (1H, dd, J ) 17.5, 1.5,
HbC8), 5.44 (1H, dt, J ) 7.5, 1.0, HC3), 5.89 (1H, dd, J ) 17.5,
11.0, HC7).
dd, J ) 10.0, 9.5, HC4′), 5.21 (1H, dd, J ) 9.5, 9.5, HC3′); 13
C
NMR (126 MHz, CDCl3, ppm) δ 19.5 (CH3-C5), 19.6 (CH3-C9)
23.7 (C7), 28.3 and 29.4 (2CH3-C1), 37.2 (C8), 37.3 (C1), 38.1
(C4), 44.2 (C2), 62.1 (C6′), 68.6 (C4′), 68.7 (C3), 71.5 (C2′/C5′),
72.9 (C3′), 76.4 (C9), 99.2 (C1′), 123.5 (C5), 137.1 (C6), 20.6-
21.5 and 169.3-170.9 (five acetates).
Spectral data for 3a : UV (MeOH) λmax 216 nm; IR (NaCl):
ν 2960, 2936, 1752, 1434, 1373, 1229, 1040 cm-1; DCI-MS
(reactant gas: NH3) pseudo-molecular ion at m/ z 602, indicat-
(2E,6E)-2,6-Dimethyl-1-hydroxyocta -2,6-dien-8-yl-O-â-D-
glucopyranoside (9) was isolated as its pentaacetate (9a ) (2
mg): UV (MeOH) λmax 210 nm; IR (NaCl) ν 2922, 1747, 1435,
1374, 1224, 1039, 907 cm-1; DCI-MS (reactant gas: NH3)
pseudo-molecular ion at m/ z 560, indicating a molecular mass
1
ing a molecular mass of 584 (C29H44O12); H NMR (360 MHz,
CDCl3, ppm, J in Hz) δ 1.00 and 1.03 (2 × 3H, 2s, 2CH3-C1),
1.23 (3H, d, J ) 6.5, H3C-C9), 1.47 (1H, dd, J ) 12.5, 2.0, Ha-
C2), 1.54 (2H, m, H2C8), 1.60 (3H, s, H3C-C5), 1.76 (1H, ddd,
J ) 12.5, 3.5, 2.0, HbC2), 1.92 (1H, dd, J ) 16.0, 2.5, HaC4),
1.95 (1H, dd, J ) 12.5, 6.5, HaC7), 2.00-2.07 (5 × 3H, 5s, five
acetates), 2.05 (1H, dd, J ) 12.5, 5.5, HbC7), 2.15 (1H, ddd, J
) 16.0, 5.5, 2.0 Hz, HbC4), 3.70 (1H, ddd, J ) 10.0, 5.0, 2.5,
HC5′), 3.90 (1H, m, HC3), 4.11 (1H, dd, J ) 12.5, 2.5, HaC6′),
4.24 (1H, dd, J ) 12.5, 5.0, HbC6′), 4.63 (1H, d, J ) 8.0, HC1′),
4.87 (1H, m, HC9), 4.95 (1H, dd, J ) 9.5, 8.0, HC2′), 5.07 (1H,
1
of 542 (C26H38O12); H NMR (360 MHz, CDCl3, ppm, J in Hz)
δ 1.66 (3H, br s, CH3-C2), 1.67 (3H, br s, CH3-C6), 2.00-2.09
(5 × 3H, 5s, five acetates), 2.10 (2H, m, H2C5), 2.17 (2H, m,
H2C4), 3.67 (1H, ddd, J ) 10.0, 5.0, 2.5, HC5′), 4.16 (1H, dd,
J ) 12.0, 2.5, HaC6′), 4.22 (1H, m, HaC8), 4.25 (1H, dd, J )
12.0, 5.0, HbC6′), 4.26 (1H, m, HbC8), 4.46 (2H, br s, H2C1),
4.54 (1H, d, J ) 8.0, HC1′), 4.99 (1H, dd, J ) 9.5, 8.0, HC2′),
5.09 (1H, dd, J ) 10.0, 9.5, HC4′), 5.21 (1H, dd, J ) 9.5, 9.5,
HC3′), 5.27 (1H, m, HC7), 5.44 (1H, m, HC3); 13C NMR (126
MHz, CDCl3, ppm) δ 14.0 (CH3-C2), 16.4 (CH3-C6), 26.0 (C4),
38.9 (C5), 62.0 (C6′), 65.3 (C8), 68.5 (C4′), 70.1 (C1), 71.3 (C2′),
71.8 (C5′), 72.9 (C3′), 98.9 (C1′), 119.5 (C7), 128.8 (C3), 130.5
(C2), 141.5 (C6), 20.6-21.0 and 169.4-171.0 (five acetates).
dd, J ) 10.0, 9.5, HC4′), 5.21 (1H, dd, J ) 9.5, 9.5, HC3′); 13
C
NMR (126 MHz, CDCl3, ppm) δ 19.6 (CH3-C5), 19.8 (CH3-C9),
23.9 (C7), 28.4 and 29.5 (2CH3-C1), 36.2 (C8), 37.6 (C1), 38.6
(C4), 45.8 (C2), 62.1 (C6′), 68.5 (C4′), 71.3 (C9), 71.4 (C2′), 71.7
(C5′), 72.8 (C3′), 73.4 (C3), 99.6 (C1′), 123.6 (C5), 137.0 (C6),
20.6-21.3 and 169.2-170.8 (five acetates).
RESULTS AND DISCUSSION
2-Phenylethyl-O-â-D-glucopyranoside (4), 2-Phenylethyl-O-
â-D-galactoside (5), and Benzyl-O-â-D-glucopyranoside (6).
Spectral data for peracetylated glucosides 4a (170 mg) and 6a
(1 mg): Williams et al., 1983; Voirin et al., 1990; Yano et al.,
1991. In order to confirm the structure of the novel peracetyl-
ated galactoside 5a (1.3 mg) an authentic specimen was
synthesized by reacting 2-phenylethanol with tetra-O-acetyl-
R-bromogalactose in the presence of Ag2CO3. The spectral data
of the synthetic product were identical with those for the
natural peracetate 5a : UV (MeOH) λmax 258 nm; IR (CHCl3)
ν 3005, 2875, 1757, 1368, 1195, 1111, 1042 cm-1; DCI-MS
(reactant gas: NH3) pseudo-molecular ion at m/ z 470, indicat-
The aqueous residue left after steam distillation of
rose petals (7 kg) was passed through a column of XAD-
2. The glycosidic isolate obtained after MeOH elution
was fractionated by ODS column chromatography. The
glycosidic subfraction that eluted with 20% MeCN was
separated by MLCCC. Enzymatic hydrolyses of ML-
CCC fractions liberated 3-hydroxy-7,8-didehydro-â-
ionol, 3-hydroxy-â-damascone, phenylethanol, benzyl
alcohol, and a series of oxygenated monoterpenyl alco-
hols. In order to isolate the intact glycoconjugates, each
glycosidic fraction was acetylated and after flash chro-
matography purified by HPLC. In this way, nine
glycosidic compounds 1-9 were obtained as their re-
spective acetates 1a -9a (cf. Figure 1).
1
ing a molecular mass of 452 (C22H28O10); H NMR (360 MHz,
CDCl3, ppm, J in Hz) δ 1.89-2.16 (4 × 3H, 4s, four acetates),
2.88-2.93 (2H, m, H2C2), 3.68 (1H, m, HaC1), 3.89 (1H, ddd,
J ) 7.0, 6.5, 1.0, HC5′), 4.13 (1H, dd, J ) 11.0, 7.0, HaC6′),
4.14 (1H, m, HbC1), 4.19 (1H, dd, J ) 11.0, 6.5, HbC6′), 4.45
(1H, d, J ) 8.0, HC1′), 4.98 (1H, dd, J ) 10.5, 3.5, HC3′), 5.21
(1H, dd, J ) 10.5, 8.0, HC2′), 5.38 (1H, dd, J ) 3.5, 1.0, HC4′),
7.18-7.30 (5H, m, aromatic protons); 13C NMR (126 MHz,
CDCl3, ppm) δ 36.0 (C2), 61.3 (C6′), 67.1 (C4′), 68.7 (C2′), 70.7
(C1 and C5′), 70.9 (C3′), 101.3 (C1′), 126.3 (C6), 128.4 (C4/
The molecular mass 580 for compound 1a was deter-
mined by means of DCI-MS. From the 1H NMR
spectrum the presence of a peracetylated â-glucose
moiety was apparent (J 1′,2′ ) 8 Hz). For the aglycon
moiety three methyl singlets (δ 1.14, 1.17, 1.88) and one